Experimental and kinetic modeling study of n-hexane oxidation. Detection of complex low-temperature products using high-resolution mass spectrometry

Belhadj, Nesrine; Lailliau, Maxence; Benoit, Roland; Dagaut, Philippe

doi:10.1016/j.combustflame.2021.111581

Cited by 15 publications

(20 citation statements)

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“…We have considered that the chemical formulae detected in this work for these isomers correspond mostly to KHPs. This assumption is based on results of simulations performed for n-hexane under conditions close to those of the present study [ 23 ] using a literature mechanism [ 18 ], including the formation of functionalized cyclic ethers (hydroperoxy and di-hydroperoxy-cyclic ethers). The model predicted 16 and 160 times less hydroperoxy and di-hydroperoxy-cyclic ethers, respectively, than KHPs.…”

Section: Resultsmentioning

confidence: 99%

“…The liquid samples were stored in a freezer (−15 °C) and analyzed by both HPLC and UHPLC coupled to high resolution mass spectrometry (Orbitrap Q-Exactive ® , Thermo Fisher Scientific, Waltham, MA, USA). This analytical protocol has been used in previous works of ours where its effectiveness was demonstrated [ 16 , 23 ]. The JSR experimental conditions are shown in Table 1 .…”

Section: Methodsmentioning

confidence: 99%

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Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

et al. 2021

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In the present study, we investigated the oxidation of 2500 ppm of di-n-butyl ether under fuel-rich conditions (φ = 2) at low temperatures (460–780 K), a residence time of 1 s, and 10 atm. The experiments were carried out in a fused silica jet-stirred reactor. Oxidation products were identified and quantified in gas samples by gas chromatography and Fourier transform infrared spectrometry. Samples were also trapped through bubbling in cool acetonitrile for high-pressure liquid chromatography (HPLC) analyses. 2,4-dinitro-phenylhydrazine was used to derivatize carbonyl products and distinguish them from other isomers. HPLC coupled to high resolution mass spectrometry (Orbitrap Q-Exactive®) allowed for the detection of oxygenated species never observed before, i.e., low-temperature oxidation products (C8H12O4,6, C8H16O3,5,7, and C8H18O2,5) and species that are more specific products of atmospheric oxidation, i.e., C16H34O4, C11H24O3, C11H22O3, and C10H22O3. Flow injection analyses indicated the presence of high molecular weight oxygenated products (m/z > 550). These results highlight the strong similitude in terms of classes of oxidation products of combustion and atmospheric oxidation, and through autoxidation processes. A kinetic modeling of the present experiments indicated some discrepancies with the present data.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

et al. 2021

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“…The present experiments were carried out in a fused silica jet-stirred reactor (JSR) setup presented earlier (Dagaut et al, 1986;Dagaut et al, 1988) and used in previous studies (Dagaut et al, 1987;Benoit et al, 2021;Belhadj et al, 2021). The two isomers α-pinene and limonene were studied separately.…”

Section: Oxidation Experimentsmentioning

confidence: 99%

“…In low-temperature combustion (cool flame) the formation of oxidized organic molecules (OOM) is mainly attributed to autoxidation reactions (Belhadj et al, 2021;Benoit et al, 2021), whereas in atmospheric chemistry, it is only relatively recently that this pathway has been considered (Vereecken et al, 2007;Crounse et al, 2013;Jokinen et al, 2014a;Berndt et al, 2015;Jokinen et al, 2015a;Berndt et al, 2016;Iyer et al, 2021). Also, it has been identified that highly oxygenated molecules (HOMs), a source of secondary organic aerosols (SOA), can result from autoxidation processes (Wang et al, 2021;Tomaz et al, 2021;Bianchi et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

“…In low-temperature combustion, when the temperature is increased, autoxidation rate goes through a maximum between 500 and 670 K, depending on the nature of the fuel (Belhadj et al, 2020;Belhadj et al, 2021), and the rate of formation of HOM also increases (Bianchi et al, 2019). Therefore, temperature has a measurable effect on the amount of HOMs formed (Wang et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

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Autoxidation of terpenes, a common pathway in tropospheric and low temperature combustion conditions: the case of limonene and α-pinene

Benoit

Belhadj

Lailliau

et al. 2021

Preprint

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Abstract. The oxidation of monoterpenes under atmospheric conditions has been the subject of numerous studies. They were motivated by the formation of oxidized organic molecules (OOM) which, due to their low vapor pressure, contribute to the formation of secondary organic aerosols (SOA). Among the different reaction mechanisms proposed for the formation of these oxidized chemical compounds, it appears that the autoxidation mechanism, involving successive events of H-migration and O2 addition, common to both low-temperature combustion and atmospheric conditions, is leading to the formation of highly oxidized molecules (HOM). In atmospheric chemistry, the importance of autoxidation compared to other oxidation pathways has been the topic of numerous studies. Conversely, in combustion, autoxidation under cool flame conditions is the main oxidation process commonly taken into account. An analysis of oxidation products detected in both conditions was performed, using the present combustion data and literature data from tropospheric oxidation studies, to investigate possible similarities in terms of observed chemical formulae of products. To carry out this study, we chose two terpenes, α-pinene and limonene (C10H16), among the most abundant biogenic components in the atmosphere, and considered in many previous studies. Also, these two isomers were selected for the diversity of their reaction sites (exo- and endo- carbon-carbon double bonds). We built an experimental database consisting of literature atmospheric oxidation data and presently obtained combustion data for the oxidation of the two selected terpenes. In order to probe the effects of the type of ionization used in mass spectrometry analyses on the detection of oxidation products, we used heated electrospray ionization (HESI) and atmospheric pressure chemical ionization (APCI), in positive and negative modes. The oxidation of limonene-oxygen-nitrogen and α-pinene-oxygen-nitrogen mixtures was performed using a jet-stirred reactor at elevated temperature (590 K), a residence time of 2 s, and atmospheric pressure. Samples of the reacting mixtures were collected in acetonitrile and analyzed by high-resolution mass spectrometry (Orbitrap Q-Exactive) after direct injection and soft ionization, i.e. (+/−) HESI and (+/−) APCI. This work shows a surprisingly similar set of chemical formulae of products, including oligomers, formed in cool flames and under simulated atmospheric conditions. Data analysis showed that a non-negligible subset of chemical formulae is common to all experiments independently of experimental parameters. Finally, this study indicates that more than 40 % of the detected chemical formulae in this full dataset can be ascribed to an autoxidation mechanism.

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Numerical treatment of turbulent reacting flows

Domingo

Bell

2023

Numerical Methods in Turbulence Simulation

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Experimental and kinetic modeling study of n-hexane oxidation. Detection of complex low-temperature products using high-resolution mass spectrometry

Cited by 15 publications

References 57 publications

Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

Autoxidation of terpenes, a common pathway in tropospheric and low temperature combustion conditions: the case of limonene and α-pinene

Numerical treatment of turbulent reacting flows

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